EP3310852B1 - Compositions d'isolation de câble comprenant un antioxydant à base de phosphore - Google Patents

Compositions d'isolation de câble comprenant un antioxydant à base de phosphore Download PDF

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EP3310852B1
EP3310852B1 EP16727595.7A EP16727595A EP3310852B1 EP 3310852 B1 EP3310852 B1 EP 3310852B1 EP 16727595 A EP16727595 A EP 16727595A EP 3310852 B1 EP3310852 B1 EP 3310852B1
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composition
antioxidant
ethylene
phosphorus
weight
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EP3310852A1 (fr
Inventor
Jeffrey M. Cogen
Manish TALREJA
Timothy J. Person
Raghunath ROY
Thomas H. Peterson
Jessica DRAZBA
Neil W. Dunchus
Gerrit Groot-Enzerink
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/307—Other macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene

Definitions

  • This invention relates to cable insulation compositions.
  • the invention relates to cable insulation compositions comprising a sulfur-containing antioxidant while in another aspect, the invention relates to cable insulation compositions comprising a sulfur-containing antioxidant and a phosphorus-containing antioxidant.
  • the invention relates to a cable comprising a sheath made from the composition.
  • Peroxide crosslinkable insulation compounds for extra high voltage (EHV) cable applications must be melt-filtered through fine screens during extrusion.
  • USP 6,187,847 and 6,187,858 describe insulation formulations that have excellent properties, except that they suffer from peroxide instability during storage and exhibit high levels of water during crosslinking.
  • USP 6,656,986 teaches that certain amine bases can mitigate these issues if they are included in the composition during extrusion.
  • manufacturing trials with the formulations described in USP 6,656,986 have identified a rapid pressure development due to fouling of the fine, e.g., less than 50 microns ( ⁇ m), screen required to achieve EHV levels of cleanliness. This results in reduced run lengths and reduced yields of EHV grade, since long runs are required to achieve high EHV yields. This screen fouling phenomenon has not been appreciated in the prior art.
  • JP-A-2011/001506 discloses a flame-retardant resin composition obtained by blending 0-30 pts. wt. of a functional group-containing olefin polymer component (D) and 3-300 pts. wt. of a flame retardant component (E) with 100 pts. wt. of a resin component.
  • the resin component comprises: 5-90 wt.% of a propylene-ethylene copolymer component (A) produced using a single-site catalyst; 5-90 wt.% of an ethylene copolymer component (B) selected from an ethylene- ⁇ - ⁇ -unsaturated carboxylic acid ester copolymer (B1), an ethylenevinyl ester component (B2), or an ethylene- ⁇ -olefin copolymer (B3) with density of 0.86 or more and less than 0.91 g/cm 3 ; and 5-90 wt.% of a polyethylene resin component (C) with density of 0.91 to 0.97 g/cm 3 .
  • the invention is a power cable insulation composition
  • a sulfur-containing first antioxidant in a relatively high amount and a phosphorus-containing second antioxidant in a relatively low amount.
  • the invention is a cable comprising a sheath made from the inventive composition.
  • inventive composition is free of polyalkylene glycol.
  • the numerical ranges in this disclosure are approximate, and thus may include values outside of the range unless otherwise indicated. Numerical ranges include all values from and including the lower and the upper values, in increments of one unit, provided that there is a separation of at least two units between any lower value and any higher value. As an example, if a compositional, physical or other property, such as, for example, temperature, is from 100 to 1,000, then all individual values, such as 100, 101, 102, etc., and sub ranges, such as 100 to 144, 155 to 170, 197 to 200, etc., are expressly enumerated.
  • compositions, process, etc. is not limited to the components, steps, etc. disclosed, but rather can include other, undisclosed components, steps, etc.
  • the term “consisting essentially of” excludes from the scope of any composition, process, etc. any other component, step etc. excepting those that are not essential to the performance, operability or the like of the composition, process, etc.
  • the term “consisting of” excludes from a composition, process, etc., any component, step, etc. not specifically disclosed.
  • Wire and like terms mean a single strand of conductive metal, e.g., copper or aluminum, or a single strand of optical fiber.
  • “Cable,” “power cable,” and like terms means at least one wire or optical fiber within a protective jacket or sheath.
  • a cable is two or more wires or optical fibers bound together, typically in a common protective jacket or sheath.
  • the individual wires or fibers inside the jacket may be bare, covered or insulated.
  • Combination cables may contain both electrical wires and optical fibers.
  • the cable, etc. can be designed for low, medium, high and extra high voltage applications.
  • low voltage means less than 5 kilovolts (kV)
  • medium voltage means 5 kV to less than 69 kV
  • high voltage means 69 kV to less than 220 kV
  • extra high voltage means greater than or equal to 220 kV.
  • Typical cable designs are illustrated in USP 5,246,783 ; 6,496,629 and 6,714,707 .
  • composition and like terms mean a mixture or blend of two or more components.
  • Polymer means a compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term polymer thus embraces the term homopolymer, usually employed to refer to polymers prepared from only one type of monomer, and the terms "interpolymer” and "copolymer”.
  • Interpolymer means a polymer prepared by the polymerization of at least two different types of monomers. These generic terms include copolymers, usually employed to refer to polymers prepared from two different types of monomers, and polymers prepared from more than two different types of monomers, e.g., terpolymers, tetrapolymers, etc.
  • Blend means a composition of two or more polymers. Such a blend may or may not be miscible. Such a blend may or may not be phase separated. Such a blend may or may not contain one or more domain configurations, as determined from transmission electron spectroscopy, light scattering, x-ray scattering, and any other method known in the art.
  • Ethylene-based polymer refers to a polymer that comprises a majority amount of polymerized ethylene based on the weight of the polymer and, optionally, may comprise at least one comonomer.
  • Tibular LDPE and like terms mean a low density polyethylene made in a process employing at least one tubular reactor.
  • Crosslinkable means that the polymer, before or after extrusion, is not cured or crosslinked and has not been subjected or exposed to treatment that has induced substantial crosslinking although the polymer comprises additive(s) or functionality which will cause or promote substantial crosslinking upon subjection or exposure to such treatment (e.g., peroxide).
  • Crosslinked means that the polymer, before or after it is extruded onto a wire or cable, was subjected or exposed to a treatment which induced crosslinking and has xylene or decalene extractables of less than or equal to 90 weight percent (i.e., greater than or equal to 10 weight percent gel content).
  • Free of polyalkylene glycol and like terms means that the inventive composition contains less than 0.1 wt%, or less than 0.05 wt%, or less than 0.01 wt%, of a polyalkylene glycol.
  • Root temperature and like terms mean 23°C.
  • the ethylenic polymers used in the practice of this invention include both homopolymers and interpolymers, random and blocky copolymers, and functionalized (e.g., ethylene vinyl acetate, ethylene ethyl acrylate, etc.) and non-functionalized polymers.
  • the ethylenic interpolymers include elastomers, flexomers and plastomers.
  • the ethylene polymer comprises at least 50, preferably at least 60 and more preferably at least 80, wt% of units derived from ethylene.
  • the other units of the ethylenic interpolymer are typically derived from one or more alpha-olefins.
  • the alpha-olefin is preferably a C 3-20 linear, branched or cyclic alpha-olefin.
  • C 3-20 alpha-olefins include propene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene.
  • the alpha-olefins also can contain a cyclic structure such as cyclohexane or cyclopentane, resulting in an alpha-olefin such as 3-cyclohexyl-1-propene (allyl cyclohexane) and vinyl cyclohexane.
  • alpha-olefins in the classical sense of the term, for purposes of this invention certain cyclic olefins, such as norbornene and related olefins, particularly 5-ethylidene-2-norbornene, are alpha-olefins and can be used in place of some or all of the alpha-olefins described above.
  • styrene and its related olefins are alpha-olefins for purposes of this invention.
  • Illustrative ethylenic interpolymers include copolymers of ethylene/propylene, ethylene/butene, ethylene/1-hexene, ethylene/1-octene, ethylene/styrene, and the like.
  • Illustrative ethylenic terpolymers include ethylene/propylene/1-octene, ethylene/propylene-/butene, ethylene/butene/1-octene, ethylene/propylene/diene monomer (EPDM) and ethylene/butene/styrene.
  • ethylenic polymers useful in the practice of this invention include high density polyethylene (HDPE); medium density polyethylene (MDPE); low density polyethylene (LDPE); very low density polyethylene (VLDPE); homogeneously branched, linear ethylene/alpha-olefin copolymers (e.g.
  • TAFMERTM by Mitsui Petrochemicals Company Limited and EXACTTM by DEX-Plastomers
  • homogeneously branched, substantially linear ethylene/alpha-olefin polymers e.g., AFFINITYTM polyolefin plastomers and ENGAGETM polyolefin elastomers available from The Dow Chemical Company
  • ethylene block copolymers INFUSETM also available from The Dow Chemical Company
  • substantially linear ethylene copolymers are more fully described in USP 5,272,236 ; 5,278,272 and 5,986,028 , and the ethylene block copolymers are more fully described in USP 7,579,408 ; 7,355,089 ; 7,524,911 ; 7,514,517 ; 7,582,716 and 7,504,347 .
  • Olefinic interpolymers of particular interest for use in the practice of this invention are LDPE, linear low density polyethylene (LLDPE) and HDPE. These ethylenic copolymers are commercially available from a number of different sources including The Dow Chemical Company under such trademarks as DOWLEXTM, ATTANETM and FLEXOMERTM.
  • One preferred polymer is a high pressure low density polyethylene (LDPE).
  • LDPE high pressure low density polyethylene
  • One conventional high pressure process is described in Introduction to Polymer Chemistry, Stille, Wiley and Sons, New York, 1962, pages 149 to 151 .
  • the high pressure processes are typically free radical initiated polymerizations conducted in a tubular reactor or a stirred autoclave. In the stirred autoclave, the pressure is in the range of 10,000 to 30,000 psi (70 to 210 kPa) and the temperature is in the range of 175 to 250°C., and in the tubular reactor, the pressure is in the range of 25,000 to 45,000 psi (170 to 310 kPa) and the temperature is in the range of 200 to 350°C.
  • the amount of ethylene polymer present in the compositions of this invention is typically of 95 to 99.9, more typically 95-99 and even more typically 96-99, wt% based on the total weight of the composition.
  • the ethylene polymer can be present as a single polymer, e.g., LDPE, or as a blend of two or more polymers, e.g., LDPE and MDPE.
  • the ethylene-based polymer is a low density polyethylene (LDPE) made in a tubular reactor.
  • LDPE low density polyethylene
  • the ethylene-based polymer has a melt index (I 2 ) from 0.1 to 100 grams per 10 minutes (g/10 min). In one embodiment, the ethylene-based polymer has an I 2 from 0.3 to 100 g/10 min, or from 0.5 to 30 g/10 min, or from 1.0 to 10 g/10 min. In one embodiment, the ethylene-based polymer has an I 2 from 0.3 to 100 g/10 min, or from 1 to 50 g/10 min, or from 2 to 20 g/10 min. Melt index is measured according to ASTM D1238, Condition 190°C/2.16 kg.
  • the ethylene-based polymer has a density greater than or equal to 0.910, or greater than or equal to 0.914, or greater than or equal to 0.916 g/cc. Density is measured by the procedure of ASTM D792, Method B. The result is recorded in grams (g) per cubic centimeter, or g/cc or g/cm 3 .
  • the ethylene-based polymer has a density less than or equal to 0.940, or less than or equal to 0.935, or less than or equal to 0.932, grams per cubic centimeter (g/cc or g/cm 3 ).
  • the ethylene-based polymer has a density from 0.910 to 0.940 g/cc. In one embodiment, the ethylene-based polymer has a density from 0.910 to 0.940, or from 0.915 to 0.935, or from 0.916 to 0.932 g/cc.
  • the ethylene-based polymer has a density from 0.912 to 0.940, or from 0.915 to 0.935, or from 0.920 to 0.930, or from 0.918 to 0.926 g/cc.
  • the ethylene-based polymer has a density of from 0.916 to 0.940, or from 0.916 to 0.921, or from 0.920 to 0.924, or from 0.923 to 0.940, g/cc.
  • the ethylene-based polymer has a density from 0.920 to 0.940 g/cc.
  • the peroxides that can be used in the practice of this invention include, but are not limited to, cyclic peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxycarbonates, peroxydicarbonates, peroxyesters, and peroxyketals.
  • the peroxide is an organic peroxide.
  • organic peroxides include dicumyl peroxide; bis(alpha-t-butyl-peroxyisopropyl)benzene; isopropylcumyl t-butyl peroxide; t-butylcumylperoxide; di-t-butyl peroxide; 2,5-bis(t-butylperoxy)-2,5-dimethylhexane; 2,5-bis(t-butylperoxy)-2,5-dimethylhexyne-3; 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane; isopropylcumyl cumylperoxide; di(isopropylcumyl) peroxide; and mixtures of two or more such initiators.
  • TRIGONOXTM 301 (3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonaan) and TRIGONOXTM 311 (3,3,5,7,7-pentamethyl-1,2,4-trioxepane), both available from Akzo Nobel, and HMCH-4-AL (3,3,6,6,9,9-hexamethyl-1,2,4,5-tetroxonane) available from United Initiators. See also WO 02/14379 and WO 01/68723 .
  • the peroxide is used in an amount from 0.2-2.5 wt%, or from 0.2-2.0 wt%, based upon the weight of composition.
  • the peroxide is used in combination with a curing coagents (and, optionally, one or more boosters or retarders).
  • Representative coagents include triallyl isocyanurate; ethoxylated bisphenol A dimethacrylate; alpha-methyl styrene dimer (AMSD); and the other coagents described in USP 5,346,961 and 4,018,852 .
  • Coagents are used, if used at all, typically in amounts of greater than 0 (e.g., 0.01) to 3, more typically 0.1 to 0.5 and even more typically 0.2 to 0.4, wt % based on the weight of the composition.
  • the sulfur-containing antioxidants used in the practice of this invention have at least one -S(CH 2 ) 2 CO 2 R group in which R is C6 to C20 alkyl. In preferred embodiments R is C 18 H 37 or C 12 H 25 .
  • sulfur-containing antioxidants include but are not limited to: dimyristyl thiodipropionate; distearyl thiodipropionate (DSTDP); dilauryl thiodipropionate (DLTDP); and pentaerythritol tetrakis (B-laurylthiopropionate). Additional examples can be found in Plastic Additives Handbook, Gachter et al, 1985 .
  • sulfur-containing antioxidants are typically used in amounts of 0.01 to 0.5 wt%, more typically in amounts of 0.05 to 0.30 wt% based on the weight of the composition.
  • Preferred embodiments include the thioesters DSTDP, DLTDP and NAUGARDTM 412S (pentaerythritol tetrakis( ⁇ -laurylthiopropionate).
  • the sulfur-containing first antioxidant is present in an amount from 0.01 to 0.5 wt%, or from 00.10 to 0.30 wt%, based on the weight of the composition.
  • the "second antioxidant" used in the practice of this invention is a phosphorus-containing antioxidant that does not contain a -S(CH 2 ) 2 CO 2 R group, wherein R is a C6 to C20 alkyl.
  • Preferred second antioxidants are phosphites, phosphonites and phosphines, with phosphites and phosphonites more preferred.
  • the second antioxidant may be a mixture of two or more phosphorus-containing antioxidants that do not contain a -S(CH 2 ) 2 CO 2 R group, wherein R is a C6 to C20 alkyl.
  • the phosphorus-containing second antioxidant does not contain sulfur.
  • Phosphorus-containing antioxidants that can be used in the practice of this invention include, but are not limited to, IRGAFOSTM 126, IRGAFOSTM 168 and IRGASTABTM 301, all available from BASF.
  • the phosphorus-containing second antioxidant is present in an amount from 0.001 to 0.05 wt% based on the weight of the composition.
  • the phosphorus-containing second antioxidant is present in an amount from 0.001 to 0.03 wt% based on the weight of the composition.
  • the phosphorus-containing second antioxidant is present in an amount from 0.001 to 0.009 wt%, or more preferably from 0.003 to 0.007 wt%, based on the weight of the composition.
  • the composition comprises a nitrogenous base.
  • the nitrogenous base is triallyl cyanurate.
  • the nitrogenous base is UVINULTM 4050 H (N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine).
  • the nitrogenous base is a hindered amine stabilizer (HAS).
  • HAS include but are not limited to: TINUVINTM XT 850, TINUVINTM 622, TINUVINTM 144, SANDUVORTM PR-31 and CHIMASSORBTM 119 FL.
  • TINUVINTM 144 is bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-n-butyl-2-(3,5-di-tert-butyl-- 4-hydroxybenzyl)malonate, has a molecular weight of about 685 grams/mole (g/mol), contains tertiary amines, and is also available from BASF.
  • SANDUVORTM PR-31 is propanedioic acid, [(4-methoxyphenyl)-methylene]-bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)ester, has a molecular weight of about 529 g/mol, contains tertiary amines, and is available from Clariant Chemicals (India) Ltd.
  • CHIMASSORBTM 119 FL or CHIMASSORBTM 119 is 10 wt% of dimethyl succinate polymer with 4-hydroxy-2,2,6,6,-tetramethyl-1-piperidineethanol and 90 wt% of N,N"'-[1,2-Ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-traizin-2-yl]imino]-3,1-propane-diyl]]bis[N'N"-dibutyl-N'N"-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)]-1 and is commercially available from BASF.
  • the optional nitrogenous base if present, is typically present in an amount of 0.001-0.01 wt%, or 0.001-0.008 wt%, or 0.002-0.004 wt%, based on the weight of the composition.
  • the nitrogenous base does not contain sulfur.
  • the nitrogenous base does not contain a -S(CH 2 ) 2 CO 2 R group, wherein R is a C6 to C20 alkyl.
  • the nitrogenous base does not contain phosphorus.
  • the nitrogenous base contains neither sulfur nor phosphorus.
  • the composition comprises a phenolic third antioxidant.
  • phenolic antioxidants include but are not limited to, hindered phenolic antioxidants such as IRGANOXTM 1010 (tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydro-cinnamate)]methane); CYANOXTM 1790 (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione); bis [(beta-(3,5-ditert-butyl-4-hydroxybenzyl)-methylcarboxyethyl)]sulphide; thiodiethylene bis(3,5-di-tert-butyl-4-hydroxy hydrocinnamate); 1,3,5-tris (3',5'-di-tert-butyl-4'-hydroxybenzyl)-2,
  • Preferred phenolic antioxidants include CYANOXTM 1790 and IRGANOXTM 1010.
  • the optional phenolic antioxidant does not contain sulfur.
  • the optional phenolic antioxidant, if present, is typically present in an amount of 0.05-0.5 wt%, or 0.1-0.3 wt% based on the weight of the composition.
  • the composition may contain additives including but not limited to processing aids, fillers, coupling agents, ultraviolet absorbers, antistatic agents, nucleating agents, slip agents, plasticizers, lubricants, viscosity control agents, tackifiers, anti-blocking agents, surfactants, extender oils, acid scavengers, and metal deactivators.
  • Additives, other than fillers are typically used in amounts ranging from 0.01 or less to 10 or more wt% based on the weight of the composition.
  • Fillers are generally added in larger amounts although they the amount can range from as low as 0.01 or less to 50 or more wt % based on the weight of the composition.
  • Examples of fillers include but are not limited to clays, precipitated silica and silicates, fumed silica, calcium carbonate, ground minerals, and carbon blacks.
  • the fillers typically have an arithmetic mean particle size larger than 15 nanometers.
  • Compounding of a cable insulation material can be effected by standard equipment known to those skilled in the art.
  • Examples of compounding equipment are internal batch mixers, such as a BANBURYTM or BOLLINGTM internal mixer.
  • continuous single, or counter and/or co-rotating twin screw, mixers can be used, such as FARRELTM continuous mixer, a WERNER AND PFLEIDERERTM twin screw mixer, or a BUSSTM kneading continuous extruder.
  • a cable containing an insulation layer comprising a composition of the invention can be prepared with various types of extruders, e.g., single or twin screw types.
  • extruders e.g., single or twin screw types.
  • a description of a conventional extruder can be found in USP 4,857,600 .
  • An example of coextrusion and an extruder therefore can be found in USP 5,575,965 .
  • a typical extruder has a hopper at its upstream end and a die at its downstream end. The hopper feeds into a barrel, which contains a screw. At the downstream end, between the end of the screw and the die, there is a screen pack and a breaker plate.
  • the screw portion of the extruder is considered to be divided up into three sections, the feed section, the compression section, and the metering section, and two zones, the back heat zone and the front heat zone, the sections and zones running from upstream to downstream.
  • the length to diameter ratio of each barrel is in the range of about 15:1 to about 30:1.
  • the cable often passes immediately into a heated vulcanization zone downstream of the extrusion die.
  • the heated cure zone can be maintained at a temperature in the range of about 200 to about 350°C, preferably in the range of about 170 to about 250°C.
  • the heated zone can be heated by pressurized steam, or inductively heated pressurized nitrogen gas.
  • MI Melt index
  • Density is measured by the procedure of ASTM D792, Method B. The result is recorded in grams (g) per cubic centimeter, or g/cc.
  • MH maximum torque is measured on a moving die rheometer (MDR) according to ASTM D-5289.
  • crosslinked samples are aged in air at 150°C for 10 and 21 days and analyzed for tensile strength and ultimate elongation on an INSTRONTM 4201 machine.
  • Tensile strength (psi) 10 days at 150°C is measured by ASTM D638.
  • Percent retained tensile strength (psi) 10 days at 150°C is measured by ASTM D638.
  • Percent retained ultimate elongation (%) 10 days at 150°C is measured by ASTM D638.
  • Plaques are crosslinked, die-cut into 3.5" diameter specimens, degassed in a vacuum over at 60°C for a minimum of 4 days, then evaluated for dissipation factor (df) using a Soken Schering Bridge set up. df Testing is carried out according to ASTM D150 at 60 Hz (at temperatures and electrical stresses indicated in the Tables).
  • AC breakdown strength (ACBD) measurements compression molded plaques are cured and cooled under pressure to a target 40 mil thickness. AC breakdown strength measurements are conducted with a Hipotronics AC test unit according to ASTM D-149. The sample is placed between two opposing cylindrical electrodes of 0.5" diameter surrounded by Exxon Univolt N61 oil. A voltage ramp of 500V/second is employed until breakdown.
  • PE1 is an additive-free LDPE (melt index 2.1 dg/min, density 0.92 g/cm 3 ).
  • PE2 is an unstabilized LDPE (PE1) that had been processed in an open mixer at 150°C for 30 minutes prior to use in the experiments.
  • CYANOXTM 1790 is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione available from Cytec Industries Inc.
  • DSTDP is distearylthiodipropionate and is available as CYANOXTM STDP from Cytec Industries, Inc.
  • IRGAFOSTM 126 is bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite available from BASF.
  • IRGAFOSTM 168 is tris(2,4-di-(tert)-butylphenyl)phosphite available from BASF.
  • IRGASTABTM 301 i.e., IRGASTABTM FS 301
  • IRGASTABTM FS 301 is a 1:1 (by weight) blend of phosphite IRGAFOSTM 168 and hydroxylamine, and it is available from BASF.
  • Dicumylperoxide is available from Akzo Nobel.
  • HOSTANOXTM P-EPQ (CAS number 119345-01-6) is a bisphosphonite antioxidant powder tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenyldiphosphonite available from Clariant.
  • Triphenylphosphine is available from Sigma-Aldrich.
  • UVINULTM 4050 (i.e., UVINULTM 4050 H) is N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine available from BASF.
  • Comparative example 1 is a prior art formulation described in USP 6,187,847 and 6,187,858 .
  • Inventive examples 1 through 3 include various embodiments of the invention with the phosphorus-containing second antioxidant at a level of 75 parts per million (ppm).
  • Comparative Examples 2 and 3 have the phosphorus-containing second antioxidant at much higher levels typical of how they are used in general polyethylene stabilization applications.
  • All formulations are prepared with PE1 (additive-free LDPE). Additives that are contained at >0.1 wt% of the formulation are added directly while the ones that are contained at ⁇ 0.1wt% of the formulation are added via masterbatches to ensure correct loading. Masterbatches are prepared in a 265g BRABENDERTM bowl at 180°C, 30 revolutions per minute (rpm), with cam blades. Additives are added when the resin starts to flux, and are mixed for 3 minutes. The compounded masterbatches are shredded and then pelletized prior to use to make the final formulations. The inventive formulations 1-8 and comparative formulations 1-5 are first compounded in a 265g BRABENDERTM bowl at 180°C, 30 rpm, with cam blades.
  • the single screw extruder contains a 'pineapple' mixing head and is operated at 100 rpm with a target melt temperature of 200°C. Strands from the extruder are water cooled and pelletized. Pellets are preheated in the oven for four hours at 70°C and are soaked with 1.8% peroxide by tumble rolling for 10 minutes followed by overnight soaking in an oven at 70°C.
  • MH maximum torque
  • Comparative Example 1 shows a large rate of MH loss of 21% per week (79% retained) while the Inventive Examples 1 through 3 show negligible loss of MH. This improved stability is achieved without any significant sacrifice in AC breakdown strength or undesired increase in dissipation factor versus Comparative Example 1.
  • Comparative Examples 2 and 3 show that when the phosphorus-containing second antioxidant is used at conventional levels a good balance of properties is not obtained (Comparative Example 2 giving insufficient cure and Comparative Example 3 having high dissipation factor).
  • Inventive Examples 4 and 5 show additional embodiments of the present invention where the phosphorus-containing second antioxidant is used in conjunction with a nitrogenous base (UVINULTM 4050).
  • Comparative Example 4 does not contain a phosphorus-containing second antioxidant.
  • Comparative Example 5 uses the phosphorus-containing second antioxidant at a conventionally high level.
  • the inventive examples give a good balance of properties while neither comparative example does. In particular, Comparative Example 4 shows 18% loss in MH after 21 days (versus 4% or less loss for the inventive examples) and Comparative Example 5 shows poor percent retained tensile strength and ultimate elongation upon heat aging at 150°C (whereas Inventive Example 5 shows good retention).
  • a multi-layer screenpack was used, the finest screen layer had a nominal opening that was less than 50 microns.
  • the first set of experiments run using this ZSK-30 accelerated test were compared to results obtained at normal additive levels in the plant in order to establish that the accelerated model test correlates with actual plant data.
  • Table 3A the ZSK-30 accelerated test correlates well with production data. That is, the results show that the trends observed in the Model test on the ZSK-30 are the same as those observed on full scale production equipment, with pressure rise increasing in the order: no base ⁇ UVINULTM 4050 ⁇ CYASORBTM 3346.
  • PE1 is an additive-free LDPE (melt index 2.1 dg/min, density 0.92 g/cm 3 ).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Claims (15)

  1. Une composition comprenant en pourcentage en poids rapporté au poids de la composition :
    (A) 95 à 99,9 % d'un polymère à base d'éthylène ;
    (B) 0,2 à 2,5 % de peroxyde ;
    (C) 0,01 à 0,5 % d'un premier antioxydant contenant du soufre ayant au moins un groupe -S(CH2)2CO2R, où R est un alkyle en C6 à C20 ;
    (D) 0,001 à 0,009 % d'un deuxième antioxydant contenant du phosphore qui ne contient pas de groupe -S(CH2)2CO2R, où R est un alkyle en C6 à C20 ;
    (E) facultativement, une base azotée organique ; et
    (F) facultativement, un troisième antioxydant phénolique qui ne contient pas de groupe -S(CH2)2CO2R, où R est un alkyle en C6 à C20.
  2. La composition de la revendication 1 dans laquelle le polymère à base d'éthylène a au moins une caractéristique parmi un indice de fluidité (I2) allant de 0,1 à 100 g/10 min mesuré selon l'ASTM D1238, condition 190 °C/2,16 kg et une masse volumique allant de 0,910 à 0,940 g/cm3 mesurée par la procédure d'ASTM D792, méthode B.
  3. La composition de la revendication 2 dans laquelle le polymère à base d'éthylène est un polyéthylène basse densité fabriqué dans un réacteur tubulaire.
  4. La composition de la revendication 1 dans laquelle le peroxyde est un peroxyde organique.
  5. La composition de la revendication 1 dans laquelle le R du groupe -S(CH2)2CO2R du premier antioxydant contenant du soufre de (C) est C18H37 ou C12H25.
  6. La composition de la revendication 1 dans laquelle le premier antioxydant contenant du soufre est au moins un parmi le thiodipropionate de dimyristyle, le thiodipropionate de distéaryle, le thiodipropionate de dilauryle et le tétrakis(B-laurylthiopropionate) de pentaérythritol.
  7. La composition de la revendication 1 dans laquelle le deuxième antioxydant contenant du phosphore est au moins un parmi un phosphite, un phosphonite ou une phosphine.
  8. La composition de la revendication 1 contenant une base azotée organique.
  9. La composition de la revendication 8 dans laquelle la base azotée est présente en une quantité allant de 0,001 à 0,009 % en poids rapporté au poids de la composition.
  10. La composition de la revendication 9 dans laquelle la base azotée organique est au moins une parmi le cyanurate de triallyle, la N,N'-bis(2,2,6,6-tétraméthyl-4-pipéridyl)-N,N'-diformylhexaméthylènediamine, et un stabilisateur aminé encombrée (HAS).
  11. La composition de la revendication 1 contenant un troisième antioxydant phénolique.
  12. La composition de la revendication 11 dans laquelle le troisième antioxydant phénolique est présent en une quantité allant de 0,05 à 0,5 % en poids rapporté au poids de la composition.
  13. La composition de la revendication 12 dans laquelle le troisième antioxydant phénolique est au moins un parmi le (tétrakis[méthylène(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]méthane) ; et la (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-diméthylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione).
  14. La composition de la revendication 1 exempte de polyalkylène glycol.
  15. Un câble comprenant une gaine d'isolation fabriquée à partir de la composition de la revendication 1.
EP16727595.7A 2015-06-17 2016-05-25 Compositions d'isolation de câble comprenant un antioxydant à base de phosphore Active EP3310852B1 (fr)

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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW202010783A (zh) 2018-09-13 2020-03-16 美商陶氏全球科技有限責任公司 含有三有機膦的基於乙烯之聚合物組合物
TW202010784A (zh) * 2018-09-13 2020-03-16 美商陶氏全球科技有限責任公司 含有氧化膦之基於乙烯之聚合物組合物
US11661531B2 (en) 2019-01-31 2023-05-30 Synthomer Adhesives Technology LLC Hygiene adhesives comprising low volatile tackifier compositions
CA3143333A1 (fr) * 2019-06-25 2020-12-30 Dow Global Technologies Llc Composition polymere a base d'ethylene contenant une triorganoaminophosphine
CN113583321A (zh) * 2020-04-30 2021-11-02 国家能源投资集团有限责任公司 可交联聚乙烯组合物及其制备方法与应用、交联聚乙烯及其应用
CN113621187B (zh) * 2020-05-07 2024-05-07 国家能源投资集团有限责任公司 可交联绝缘聚烯烃组合物及其制备方法与应用、交联绝缘聚烯烃及其应用
WO2022139885A1 (fr) * 2020-12-22 2022-06-30 Dow Global Technologies Llc Résines de polyéthylène modifiées et leur procédé de fabrication
WO2024006695A1 (fr) * 2022-06-29 2024-01-04 Dow Global Technologies Llc Compositions polymères stabilisées par ultraviolets

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4018852A (en) 1974-11-27 1977-04-19 Union Carbide Corporation Composition with triallyl compounds and process for avoiding scorching of ethylene polymer composition
US4857257A (en) * 1983-06-13 1989-08-15 Allied-Signal Inc. Rotationally molding crosslinkable polyethylene composition
JPH0832806B2 (ja) * 1987-01-09 1996-03-29 チッソ株式会社 架橋エチレン系重合体の製造法
US4857600A (en) 1988-05-23 1989-08-15 Union Carbide Corporation Process for grafting diacid anhydrides
US5272236A (en) 1991-10-15 1993-12-21 The Dow Chemical Company Elastic substantially linear olefin polymers
US5246783A (en) 1991-08-15 1993-09-21 Exxon Chemical Patents Inc. Electrical devices comprising polymeric insulating or semiconducting members
US5783638A (en) 1991-10-15 1998-07-21 The Dow Chemical Company Elastic substantially linear ethylene polymers
US5278272A (en) 1991-10-15 1994-01-11 The Dow Chemical Company Elastic substantialy linear olefin polymers
US5346961A (en) 1993-04-07 1994-09-13 Union Carbide Chemicals & Plastics Technology Corporation Process for crosslinking
US5575965A (en) 1995-05-19 1996-11-19 Union Carbide Chemicals & Plastics Technology Corporation Process for extrusion
JPH10316807A (ja) * 1997-05-20 1998-12-02 Nippon Unicar Co Ltd 水架橋性含浸樹脂およびこれを用いた水架橋成形物
SE9703844D0 (sv) * 1997-10-22 1997-10-22 Borealis As Composition for electric cables
JP3959183B2 (ja) 1998-09-09 2007-08-15 日本ユニカー株式会社 電気絶縁組成物および電線ケーブル
US6496629B2 (en) 1999-05-28 2002-12-17 Tycom (Us) Inc. Undersea telecommunications cable
US6187847B1 (en) 1999-07-22 2001-02-13 Union Carbide Chemicals & Plastics Technology Corporation Polyethylene crosslinkable composition
WO2001068723A2 (fr) 2000-03-16 2001-09-20 Basell Polyolefine Gmbh Procede de production de polyethylene
PL360880A1 (en) 2000-08-15 2004-09-20 Akzo Nobel N.V. Use of trioxepans in the process to make high-solid acrylic, styrenic, and ldpe-type resins
US6656986B2 (en) 2001-03-01 2003-12-02 Union Carbide Chemicals & Plastics Technology Corporation Polyethylene crosslinkable composition
US6714707B2 (en) 2002-01-24 2004-03-30 Alcatel Optical cable housing an optical unit surrounded by a plurality of gel layers
US7582716B2 (en) 2004-03-17 2009-09-01 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for blown films with high hot tack
US7579408B2 (en) 2004-03-17 2009-08-25 Dow Global Technologies Inc. Thermoplastic vulcanizate comprising interpolymers of ethylene/α-olefins
US7355089B2 (en) 2004-03-17 2008-04-08 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates
US7504347B2 (en) 2004-03-17 2009-03-17 Dow Global Technologies Inc. Fibers made from copolymers of propylene/α-olefins
US7514517B2 (en) 2004-03-17 2009-04-07 Dow Global Technologies Inc. Anti-blocking compositions comprising interpolymers of ethylene/α-olefins
US7524911B2 (en) 2004-03-17 2009-04-28 Dow Global Technologies Inc. Adhesive and marking compositions made from interpolymers of ethylene/α-olefins
CN101802079A (zh) * 2007-07-13 2010-08-11 陶氏环球技术公司 包含不含硅烷官能度的高压聚烯烃的低介电损失动力电缆护套
JP2011001506A (ja) * 2009-06-22 2011-01-06 Japan Polypropylene Corp 難燃性樹脂組成物及びそれよりなる成形体
CN101724192A (zh) * 2009-12-15 2010-06-09 上海新上化高分子材料有限公司 中高压抗水树绝缘电缆料及其制备方法
BR112012015319B1 (pt) * 2009-12-21 2021-09-28 Union Carbide Corporation Composição e revestimento isolante para cabo de média voltagem
CN102532638B (zh) * 2010-12-10 2014-06-18 浙江万马高分子材料有限公司 高压电缆用绝缘材料及制备方法
CN102643472A (zh) * 2012-04-19 2012-08-22 上海新上化高分子材料有限公司 中高压电力电缆用可化学交联聚乙烯绝缘塑料及制备方法
CN104903395B (zh) * 2012-12-29 2018-07-13 陶氏环球技术有限责任公司 可交联聚合性组合物、制造所述聚合性组合物的方法以及由其制成的物品
CN103289162B (zh) * 2013-03-28 2016-04-27 西安交通大学 一种抗水树型聚烯烃电缆料及其制备方法
CN103694540A (zh) * 2013-12-16 2014-04-02 上海新上化高分子材料有限公司 海洋工程电缆用柔软高机械强度中压绝缘料及其制备方法
CN104558759A (zh) * 2014-11-28 2015-04-29 上海新上化高分子材料有限公司 海底电缆用可化学交联聚乙烯绝缘塑料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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US10093788B2 (en) 2018-10-09
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JP6857621B2 (ja) 2021-04-14
CN107771197A (zh) 2018-03-06
KR102537800B1 (ko) 2023-05-31
US20180215899A1 (en) 2018-08-02
KR20180018650A (ko) 2018-02-21
MX2017015816A (es) 2018-04-10
BR112017026118B1 (pt) 2022-01-04
CA2989418A1 (fr) 2016-12-22
WO2016204951A1 (fr) 2016-12-22
CA2989418C (fr) 2023-09-12
CN107771197B (zh) 2020-12-01

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